CN101038852B - Multipurpose large-capacity linear ion trap and integrated electrode processing method - Google Patents
Multipurpose large-capacity linear ion trap and integrated electrode processing method Download PDFInfo
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Abstract
The invention relates to a large capacity linear ion well which can be applied on various analysis aims and an electrode processing method which realizes integration of high accuracy and precision processing and installing. The linear ion well includes an ion capture chamber, RF electrode, and DC electrode, wherein, RF electrode is comprised by plural parts thereby dividing the ion capture chamber into plural sub-regions, thus, plural mass spectrometry procedures can be realized. The RF electrode of the ion well can be made in an integration processing manner of processing nonmetallic substrate first and then coating a metallic membrane on the surface thereof, at last, removing the metallic membrane of insulation region according to the requirement of the sub-electrodes. The multipurpose large capacity linear ion well provides an implementation scheme having characters of high applicability, various uses, low cost, easy processing and installation for the development of ion well quality analyzer and mass spectrograph.
Description
Technical field
The present invention relates to the analytical technique of mass spectrum field, relate in particular to a kind of large-capacity linear ion trap and integrated electrode processing method thereof, particularly relate to a kind of large-capacity linear ion trap and a kind of integrated electrode processing method that is easy to realize processing of high accuracy high precision and assembling that can be used for multiple analysis purpose.
Background technology
Quadrupole ion trap is a kind of special device, it both can be used as the ion storage device, in cycle regular hour, gas ion is limited in the quadrupole field zone in the ion trap, the mass analyzer that can be used as mass spectrometer is again carried out mass spectral analysis, and has sizable mass range and variable mass resolution.Four utmost point electrostatic fields in the ion trap produce by insert RF radio-frequency voltage, DC direct voltage or the composite signal of the two on each utmost point bar of ion trap device.Traditional ion trap is made up of two parts electrode, i.e. ring electrode and endcap electrode, and in order to produce significant quadrupole field, typical electrode shape is a hyperbolic type.
Early stage ion trap is a three-dimensional ion trap, and its quadrupole field produces at r and z (in the polar coordinate system) direction, and ion is subjected to the effect of linear force in this quadrupole field, thereby can and be stored in this ion trap the ion trap in certain mass-to-charge ratio m/z scope.Most typical three-dimensional ion trap is made up of three hyperbolic electrodes, i.e. a ring electrode and two endcap electrodes, and this type of device is commonly referred to Paul type ion trap or quadrupole ion trap.Cylindrical ion trap is a kind of simpler three-dimensional ion trap, is made up of the inner surface ring electrode that is the face of cylinder and the endcap electrode of two slab constructions.The defective of Paul type ion trap and cylindrical ion trap maximum is that the number of ions of catching in the trap is few, and is lower for its capture rate of incident ion of ionization outside trap.
Another kind of ion trap---linear ion hydrazine has appearred in recent years.Linear ion hydrazine is made up of that prolong and a plurality of utmost point bars parallel placement, this utmost point leverage will be determined the volume of ion trap, by on utmost point bar, inserting RF radio-frequency voltage and DC direct voltage, can on perpendicular to the plane of ion trap central shaft, produce two-dimentional quadrupole field, owing to only realize the strong-focusing of ion in two dimension, the ion of being caught can distribute near central shaft, has improved the ion trap number greatly.United States Patent (USP) 5420425 has been described a kind of two-dimensional linear ion trap of being made up of three groups of quadrupole rods, and one group of middle quadrupole rod has designed slit as main quadrupole rod on the wherein a pair of main pole bar, and ion can be realized injecting and outgoing by this slit; Two groups of quadrupole rods at two ends both can be implemented in the motion of catching ion in the axial restraint trap, can improve the quadrupole field in the main quadrupole rod again, when each utmost point bar all adopts hyperbolic utmost point bar, can obtain the quadrupole field of near ideal.
In above-mentioned each ion trap, except that cylindrical ion trap, all need mechanical processing process accurately, as processing, assembling etc., and high-accuracy mechanical processing is quite complicated like this.Especially adopt the ion trap of hyperboloid electrode, under the prerequisite that guarantees machining accuracy, mounting technology just becomes a final big bottleneck that influences the Instrumental Analysis performance, also therefore becomes one of principal element of restriction small ion trap mass analyzer development.
Ion trap has the function that selectivity stores, separates and analyze concurrently, makes ion strap mass analyzer carry out mass spectrum-mass spectrum experiment (MS
n) aspect has advantageous advantage.Just can carry out MS although utilize single ion trap
nExperiment, but development along with electron spray ionisation (ESI) and substance assistant laser desorpted ionized ionization modes such as (MALDI), mass spectral analysis is extensively and profoundly in the analysis of big molecule complex sample, this has just proposed new demand to ion strap mass analyzer, utilizes the technology of a plurality of ion traps realization combined ionic traps also to arise at the historic moment.United States Patent (USP) 6483109B2 has proposed a kind of multi-stage ms instrument, in this instrument, with a plurality of ion traps according to tandem-in-space, be that end to end mode is formed multistage ion trap space, adopt termination electrode to separate between at different levels, ion circulates between at different levels in proper order, realizes the function of storing, separate, dissociate or analyzing respectively.United States Patent (USP) 6838666B2 has proposed a kind of rectangle linear ion hydrazine (RIT) that utilizes four rectangular flat electrodes to surround, and the RIT combined ionic trap that has proposed to utilize three above RIT to form, each RIT unit all comprises four plate electrodes and a pair of end cap, and MS is carried out in ion order circulation in this combined ionic trap
nExperiment.Knockdown ion trap is for utilizing MS in the fields such as research complex sample, especially ion chemistry, large biological molecule and pharmacy
nThe qualitative research that realizes molecular structure provides a kind of new powerful mass spectral analysis instrument.But, existing combined ion well structure relative complex, add the high-accuracy assembly problem that relates to man-hour between multistage electrode, the end cap in design, ion can produce losses of ions by the aperture of dull and stereotyped end cap when next stage transmits, thereby influences the resolution and the sensitivity of ion strap mass analyzer.
In sum, no matter existing linear ion trap mass analyzer is single ion trap or combined ion trap, all needs high accuracy mechanical processing and assembling.The MS of single ion trap
nFunction is single relatively, complicated operation even can't finish analysis task when the application such as ion/ion reaction of carrying out complex sample, various product.The combined ion trap utilizes different compound modes to can be used for carrying out the plural serial stage analysis of complex sample, various product, but its complex structure, the ion flow passband is also influenced, the process and assemble relative complex.Along with subject development such as biology, pharmacy, ion chemistries, existing ion strap mass analyzer all more or less all exposes its limitation.Therefore, explore a kind of structure and simplify, have concurrently simultaneously linear ion hydrazine and a kind of electrode processing method that is easy to the electrode assembling of multiple analytic function relatively, will promote the development of small ion trap mass analyzer effectively, thereby promote subject development such as biology, pharmacy, ion chemistry.
Summary of the invention
One of the technical problem to be solved in the present invention provides a kind of structure to be simplified relatively, can be used for the large-capacity linear ion trap of multiple analysis purpose.
Two of the bright technical problem that will solve of we provides a kind of be easy to realize processing of high accuracy high precision and the integrated electrode processing method that assembles.
For solving first above-mentioned technical problem, the present invention proposes a kind of multipurpose large-capacity linear ion trap.
This multipurpose large-capacity linear ion trap comprises: by at least four RF electrode and the determined ion trap of pair of end electrode chambers that are parallel to ion trap central shaft z axle; RF radiofrequency signal and DC direct current signal.
The maximum difference of the present invention and existing linear ion hydrazine is that the RF electrode group of ion trap can be divided into two parts at least along the z direction, the electrode unit of single part is called sub-RF electrode group, have at least on the sub-RF electrode in each sub-RF electrode group and offer slit, slit can be used for also can be used for sample or ion and radially leaving ion trap radially with sample or in importing trap.
Among the application, the RF electrode that is parallel to central shaft z axle can be divided into x electrode pair and y electrode pair, and each electrode is placed according to x-y-x-y mode alternate intervals 90 degree, thereby defines an ion trap zone; The RF radio-frequency power supply is connected to x and/or y electrode pair, thereby produces RF ion trap electric field in the xy plane; Termination electrode is positioned at x and two ends, y electrode pair defined ion trap zone; It is right that the DC DC power supply is connected to termination electrode, provides between two termination electrodes and catch potential energy well along the axial DC of z.RF electrode group is separated into two parts at least, and the ion trap zone also is divided into a plurality of subregions with regard to corresponding, and each part of RF electrode group all is connected with RF radiofrequency signal and/or DC direct current signal.AC voltage can be connected to the x electrode pair or the y electrode pair of sub-RF electrode group, is used for exciting or evict from ion along x direction or y direction; Also can be connected to and realize on the termination electrode exciting or evict from ion along the z direction.Can provide corresponding analytic function by the electrical quantity (as the RF/DC/AC parameter) that each sub-RF electrode is set according to analyzing needs,, also can have multinomial function wherein simultaneously concurrently as selectivity storage, separation, ionic reaction or analyzed area.
The termination electrode of multipurpose large-capacity linear ion trap can be the plate electrode of placing along the xy plane, also can be the multipole bar that is parallel to the z axle, can also be the combination of pole plate and multipole bar.At termination electrode is in the situation of plate electrode, can offer aperture or slit on a dull and stereotyped termination electrode therein, also can on two dull and stereotyped termination electrodes, all offer aperture or slit, aperture of being opened or slit can be used for the importing of sample or ion, also can be used for sample or ion leaves ion trap.
Slit on the RF electrode has the multiple scheme of offering, can on the x electrode pair of each sub-RF electrode group, all offer slit, also can on the y electrode pair of each sub-RF electrode group, all offer slit, can also open at least under the prerequisite of a slit in each sub-RF electrode group of assurance, adopt the composite type slit between each sub-electrode group, perhaps open electrode, perhaps open electrode, realize combination in any as required at y at x.Slit on the RF electrode and the aperture on the termination electrode or slit all can be used as the inlet or the outlet of sample or ion, by making up multiple entry or the multiple exit analytical model that can realize along x, y or z direction.
Multipurpose large-capacity linear ion trap can use outer ion source ionization mode, also can use internal ion-source ionization mode, the ionization mode that can also use inside and outside ion source to combine.The multiple entry pattern of ion trap makes and can link to each other with two or more ion sources.Outside a plurality of under the ionogenic situation, ionogenic ion transfer system can be by the aperture/slit on the end cap with in the iontophoresis trap, also can be by the slit on the RF electrode with in the iontophoresis trap.When ion trap is carried out quality analysis, can adopt a plurality of detectors to realize ion detection.
For solving aforesaid second technical problem, the present invention proposes a kind of integrated electrode processing method.
The basic step of integrated electrode processing method comprises: at first adopting nonmetallic materials is matrix, be processed into required RF electrode shape, be covered with the layer of metal electrically conductive film on the surface of nonmetal electrode matrix then, last position in the needs insulation is ground off or car falls metal film.In this processing method, nonmetallic materials can be ceramic materials, and it is the conductor material of main component that metal film can adopt with the gold.
Integrated electrode processing method is particularly useful for electrode to be divided into the situation of a plurality of parts, and the RF electrode of the multipurpose large-capacity linear ion trap that the application proposed just can adopt this method to process.In the existing processing method, usually adopt metal material directly to process the electrode of various piece, adopt insulating material with the each several part combine and assemble then, this just requires to possess accurate mounting technology, and this technology has become a big bottleneck of present ion trap processing and manufacturing.Adopt incorporate processing mode, can guarantee the uniformity of various piece on the same electrode, thereby reduce the difficulty of mounting technology.
The multipurpose large-capacity linear ion trap that the application proposed just can be realized the expansion of ion trap analytic function by RF electrode group is divided into a plurality of parts along the z direction, according to the needs of analysis purpose, analytical method is set just can carries out required analysis experiment.This ion trap has adaptability widely, when only utilizing one of them subregion as analyzed area, just is equivalent to existing single ion strap mass analyzer; When utilizing a plurality of subregion collaborative work, by defining the function of each sub regions, as selectivity storage, separation, ionic reaction or analyzed area, or its combination, just can provide multiple mode of operation, comprise existing spatial order circulation MS
nAnalyze experiment, the tandem-in-space combined MS that connects with the time
nArray analysis experiment.Knockdown mode of operation not only realizes existing MS
nAnalytical technology, the MS in more exploring
nAnalytical method provides a strong tool, helps scientists to carry out structure of matter research.
Compare with the combined ion trap that existing a plurality of ion traps directly are composed in series, the structure of the multipurpose large-capacity linear ion trap that the application proposes is more simplified, only come comparison from configuration aspects, as if just omitted termination electrode and directly a plurality of RF electrode groups are together in series, yet such omission but can and be made the change that bring brilliance for control, the debugging of ion trap.Aspect control circuit, can save DC or AC signal on the termination electrode between the adjacent trap, when the RF electrode only is divided into two parts, can save the signal of an endcap electrode, as if its superiority is obvious inadequately, but the part number that is divided into along with the RF electrode increases, this advantage is just particularly remarkable.The instrument testing aspect, few termination electrode, the trap internal loss of ion will correspondingly reduce, thereby reduces by an influencing factor to instrument performance.At manufacture view, there is not the separation of end cap, just can adopt the processing mode of integrated electrode, reduce the difficulty of assembling aspect.
In a word, the multipurpose large-capacity linear ion trap that the application proposed can roll into one the function of existing single ion trap and combined ion trap, has extensive applicability, for the development in fields such as biology, pharmacy, ion chemistry provides a kind of strong research tool, simultaneously, because its structure is simple relatively, alleviated the task complexity of mass spectrometer control and debugging, and can adopt integral processing method, thereby reduce the assembly difficulty of ion trap.This linear ion hydrazine also will promote the development of the analytical technology in fields such as biology, pharmacy, ion chemistry energetically for the development of ion strap mass analyzer and mass spectrometer provides that a kind of adaptability is strong, diverse in function, be easy to process and assemble, the relative cheap practicable embodiment of cost.
Description of drawings
Fig. 1: the RF electrode comprises the schematic diagram of the multipurpose large-capacity linear ion trap of two parts.
Fig. 2: the RF electrode comprises the schematic diagram of the multipurpose large-capacity linear ion trap of three parts.
Fig. 3: typical R F electrode cross-section schematic diagram.
Fig. 4: with the quadrupole rod is the schematic diagram of the multipurpose large-capacity linear ion trap of termination electrode.
Fig. 5: with plate electrode and quadrupole rod is the schematic diagram of the multipurpose large-capacity linear ion trap of termination electrode.
Fig. 6: dual ion sources dual detector ion trap quality analysis system schematic diagram.
Fig. 7: multi-ion source multi-detector ion trap quality analysis system schematic diagram.
Fig. 8: the schematic diagram that adopts the big consumption linear ion hydrazine of multipurpose of integrated processing mode.
Embodiment
Below in conjunction with accompanying drawing the application is described in further detail.
The application has proposed a kind of multipurpose large-capacity linear ion trap.
Shown in Figure 1 is the multipurpose large-capacity linear ion trap that its RF electrode group comprises two parts, and DC, AC and RF voltage are connected respectively on utmost point bar and the termination electrode, are used to catch and analyze ion.X electrode 1,2 and y electrode 3,4 are parallel to the z axle and place, RF electrode group is divided into two parts along the z direction, in the xy plane, place according to each interval 90 degree of 1-3-2-4 clockwise direction, x electrode pair and y electrode pair have defined the ion trap zone of this linear ion hydrazine, and sub-RF electrode group I and sub-RF electrode group II correspond respectively to ion trap subregion I and subregion II.All offered slit 7 and 8 on the x electrode pair of two sub-RF electrode groups, slit can be used for also can be used for sample or ion and radially leaving ion trap radially with in sample or the iontophoresis trap.The RF radio-frequency voltage is connected respectively to the y electrode pair, also can be connected to x and y electrode pair simultaneously, generates the RF ion trap electric field in the xy plane in the pairing ion trap subregion of sub-RF electrode group.All be connected to the DC direct current signal on two sub-RF electrode groups.Termination electrode 5 and 6 lays respectively at the two ends in x and the defined ion trap of y electrode pair zone; Insert the DC direct voltage on the termination electrode.Adjust the DC dc voltage value on termination electrode and the sub-RF electrode group, can obtain two zones between the termination electrode and catch electric field along the axial DC of z, the DC current potential of two sub-RF electrode groups can be identical, also can be inequality, produce the difference level thus and catch subregion, can be implemented in that two sub regions are caught the ion of opposed polarity simultaneously respectively or from the ion of two samples.AC voltage is connected on x electrode pair or the y electrode pair, as the AC resonant excitation signal between x electrode pair or the y electrode pair, thereby realizes excited ion in the trap along x direction or y direction.Can provide corresponding analytic function by the electrical quantity (as the RF/DC/AC parameter) that each sub-RF electrode is set according to analyzing needs, as selectivity storage, separation, ionic reaction or analyzed area, perhaps a sub regions has multinomial function wherein simultaneously concurrently.
Utilize multipurpose large-capacity linear ion trap single to catch the groundwork process that subregion carries out quality analysis be that sample gas to be analyzed generates analyte ions in the trap internal ionization, or sample to be analyzed injects analyte ions in the trap after the ionization outside trap, the bump kinetic energy decay of ion and buffer gas, and caught electric field and DC by RF and catch electric field and be limited in the ion trap zone in the trap, after ion is hunted down, the signal of AC or other waveforms is linked on utmost point bar or the termination electrode, can realize the quality Selective Separation of ion or excites.Utilize AC to excite alternative to excite object ion, its kinetic energy is increased, the collision induced dissociation (CID) that bumps and can realize ion in cushion gas behind the object ion acquisition kinetic energy utilizes CID can carry out MS
nExperiment.When AC voltage was received on the end cap pole plate, scanning RF amplitude can realize that ion evicts ion trap along the z direction of principal axis from by aperture on the end cap pole plate or slit.When AC voltage was received sub-x or y electrode pair, scanning RF amplitude can realize that ion evicts ion trap along x or y direction from by the slit on sub-x electrode or the sub-y electrode.The outer ion detector of trap detects dispossessed ion and just can obtain corresponding mass spectrogram.
The basic functional principle that multipurpose large-capacity linear ion trap single catches subregion is identical with existing linear ion hydrazine theory.When the DC DC component that group RF electrode group is inserted was zero, operating state was corresponding to the q axle in the stability diagram.The initial RF amplitude will determine the lower limit of stabilizing ion mass-to-charge ratio, and all mass-to-charge ratioes all can be caught by ion trap more than or equal to the ion of this lower limit, are stored in the ion trap.By being set, initial RF amplitude on the sub-RF electrode group can adjust the quality lower limit of the stored ion of this subregion.
Realize that ion isolation has two kinds of working method: RF/DC to separate and separates with the AC waveform.RF/DC separates based on the ion motion stability diagram, becomes instability in stability diagram boundary motion state by stable by making ion, thereby unstable ion is launched ion trap.The course of work that RF/DC separates is to select to be retained in ion in the ion trap according to the needs that separate, calculate keep the state parameter (a of ion
i, q
i), make its state point (a
i, q
i) drop near the stable triangle summit, adjust the RF component on the y utmost point bar and insert the DC component simultaneously according to result of calculation then, make the object ion state point become (a
i, q
i), at this moment, other ion just falls into unstable region, thereby object ion and other ion isolation are come.
It is to be the basis with the pass between ion motion fundamental frequency and the ionic condition that the AC waveform separates, and excites back z direction amplitude response to be proportional to the Fourier conversion of this excitation waveform itself, and the ion response is irrelevant with the ion axial oscillation frequency, and also the mass-to-charge ratio with ion has nothing to do.Suffered only exciting determined by the amplitude size that excites under mass-to-charge ratio institute respective frequencies mass-to-charge ratio by the ion of m/z.With the ion motion fundamental frequency as tie, do not need ion trajectory calculated accurately and just can determine to be excited the axial amplitude of back ion, as long as corresponding electrode on insert and separate the corresponding AC waveform of purpose, can realize simultaneously to the selective excitation of a plurality of object ions with evict from.
In multipurpose large-capacity linear ion trap, usually need the single target ion is carried out the selectivity resonant excitation and evicts from, be the AC resonant excitation and evict from, it is the special case that the AC waveform separates in essence, i.e. object ion motion fundamental frequency is a certain frequency values, but not a certain frequency band.In linear ion hydrazine as shown in Figure 6, the AC signal is added in two x and extremely goes up, can realize ion along the resonant excitation of x direction with evict from.
The quality analysis of multipurpose large-capacity linear ion trap is by ion being selected, made object ion become instability by stable, thereby evict it from ion trap, realizing ion detection.The unstable detection of selectivity can be divided into the border emission and evict dual mode from AC resonance.The border emission, be as the working point with the stability boundaris point on the stability diagram q axle, the dc voltage amplitude is zero, by scanning RF voltage amplitude (scanning of rising), make ion enter labile state according to mass-to-charge ratio order from small to large, unstable ion will be evicted from ion trap, arrive the outer ion detection system of trap, reception is also amplified the corresponding signal of telecommunication, just can obtain corresponding mass spectrogram.The relation of having utilized between ion motion fundamental frequency and the ion state of living in is evicted in AC resonance from, by scanning RF, change the motion fundamental frequency of ion, when the fundamental frequency of ion equates with the frequency of AC signal, ion will enlarge markedly rapidly at the amplitude of x direction, leave ion trap from the slit of x pole plate central authorities, enter outer detecting circuit.
Often need the structure of material to be identified MS carrying out mass spectral analysis
nExperiment is exactly the basis of this analysis.In MSn experiment, need make object ion be cracked into fragment ion, by fragment ion is carried out the kind that scanning of the mass spectrum is determined fragment ion, thereby determine the composition structure of object ion.The cracking of object ion has multiple implementation, and commonly used has: the CID that utilizes ion and cushion gas to bump to produce, utilize electron capture cracking (ECD) that the ion ionic reaction takes place and electron transfer cracking (ETD) etc.In multipurpose large-capacity linear ion trap, each is caught subregion and all can be used as an independently reative cell, and the design of a plurality of subregions is MS just
nSufficient basic condition is provided,, can have carried out the MS of various procedures by distributing each regional function
nExperiment.
Each of multipurpose large-capacity linear ion trap is caught subregion and is all possessed the independent function that realizes selectivity ion storage, separation, reaction/cracking, analysis, when a plurality of when catching the subregion collaborative work, go out multiple analytic process/method with regard to capable of being combined, this also makes this linear ion hydrazine have adaptability widely, and possesses diversified function.
Shown in Figure 2 is the multipurpose large-capacity linear ion trap that the RF electrode is divided into three parts, its structure and voltage signal connected mode and Fig. 1's is similar, just increased a sub-RF electrode group III, a corresponding ion trap subregion III and one group of voltage signal that is connected to sub-RF electrode group III of having increased than Fig. 1.Because increased an ion trap zone subregion III, the working method of this multipurpose large-capacity linear ion trap just has more variation.
The RF electrode of multipurpose large-capacity linear ion trap can adopt the various electrode shapes that produce quadrupole field, the hyperbolic type electrode shown in the a-d of Fig. 3, and cylinder electrode can resolve to the optimization field pattern electrode of a plurality of thin layer elements, rectangular flat electrode etc.
In multipurpose large-capacity linear ion trap, termination electrode can be the plate electrode of placing along the xy plane 5 and 6, as depicted in figs. 1 and 2; Also can be the multipole bar that is parallel to four electrodes compositions of z axle, as termination electrode I and the termination electrode II employing quadrupole rod of Fig. 4, each electrode be placed according to each interval 90 degree in the xy plane; Can also be the combination of plate electrode and multipole bar, as shown in Figure 5.Dc voltage can be inserted on the dull and stereotyped termination electrode, RF voltage or dc voltage or the combination of the two can be inserted on the multipole rod end electrode.The main effect of termination electrode is to produce along the axial potential energy well of z, on the z direction with ion limit in the trapping region of ion trap.
Shown in Fig. 1,2,4 and 5, can on sub-RF electrode, offer the slit (7 and 8) that is parallel to the z axle in the linear ion hydrazine, and on sub-x or y electrode pair, insert the AC signal, realize evicting ion trap from along x or y direction excited ion or with ion; Also can on dull and stereotyped termination electrode, offer aperture or slit, realize evicting ion trap from along z direction excited ion or with ion; Also above-mentioned each mode combination in any can be realized multi-direction excited ion or evicts ion from ion trap.
Slit on the RF electrode has the multiple scheme of offering, can on the x electrode pair of each sub-RF electrode group, all offer slit, also can on the y electrode pair of each sub-RF electrode group, all offer slit, can also open at least under the prerequisite of a slit in each sub-RF electrode group of assurance, adopt the composite type slit between each sub-electrode group, perhaps open electrode, perhaps open electrode, realize combination in any as required at y at x.Slit on the electrode and the aperture on the termination electrode or slit all can be used as the inlet or the outlet of sample or ion, by making up multiple entry or the multiple exit analytical model that can realize along x, y or z direction.
Multipurpose large-capacity linear ion trap can use outer ion source ionization mode, also can use internal ion-source ionization mode, the ionization mode that can also use inside and outside ion source to combine.The multiple entry pattern of ion trap makes and can link to each other with two or more ion sources.Outside a plurality of under the ionogenic situation, ionogenic ion transfer system can be by the aperture/slit on the end cap with in the iontophoresis trap, also can by on the RF electrode slit with in the iontophoresis trap.Shown in Figure 6 is a dual ion sources dual detector multipurpose large-capacity linear ion trap, the ion that two ion sources the produce aperture from two dull and stereotyped termination electrodes respectively enters in the trap, when being carried out quality analysis, adopt in ion radially ion to evict from, outside two slits, be provided with detector, detect the ion of from two sub regions, evicting from respectively.Shown in Figure 7 is the combination schematic diagram of a multi-ion source multi-detector multipurpose large-capacity linear ion trap, can connect corresponding device thereof at each ion source or detector location according to concrete needs, realize that at space three-dimensional knockdown multi-ion source detects the mass spectral analysis scheme more.
At the multipurpose large-capacity linear ion trap of said structure, by RF electrode group is divided into a plurality of parts along the z direction, just can realize the expansion of ion trap analytic function, according to the needs of analysis purpose, analytical method is set just can carries out required analysis experiment.This ion trap has adaptability widely, when only utilizing one of them subregion as analyzed area, just is equivalent to existing single ion strap mass analyzer; When utilizing a plurality of subregion collaborative work, by defining the function of each sub regions, as selectivity storage, separation, ionic reaction or analyzed area, or its combination, just can provide multiple mode of operation, comprise existing spatial order circulation MS
nAnalyze experiment, the tandem-in-space combined MS that connects with the time
nArray analysis experiment.Knockdown mode of operation not only realizes existing MS
nAnalytical technology, the MS in more exploring
nAnalytical method provides a strong tool, helps scientists to verify or realize the possible technology path of more structure of matter research.
The invention allows for a kind of integrated electrode processing method.
The basic step of integrated electrode processing method comprises: at first adopting nonmetallic materials is matrix, be processed into required RF electrode shape, as hyperbolic electrode, cylinder electrode, rectangular flat electrode, can resolve to the optimization field pattern electrode of a plurality of thin layer elements, be covered with the layer of metal electrically conductive film on the surface of this nonmetal electrode matrix then, last position in the needs insulation is ground off or car falls metal film.In this processing method, nonmetallic materials can be selected ceramic material for use, and it is the conductor material of main component that metal film can be selected for use with the gold, as highly purified gold.
Shown in Figure 8 is the multipurpose large-capacity linear ion trap that the RF electrode adopts integral method to process, electrode be shaped as hyperbolical, the RF electrode is divided into three parts, golden film is represented to be covered with in dark surface, white surface represents to remove the ceramic matrix surface of golden film, all offered slit on the x electrode of various piece, three slits on the same x electrode fuse, promptly in the course of processing of ceramic matrix electrode, offer a long slit, also slit has been divided into three parts when in subsequent step, electrode being divided into three parts.The processing method of once cracking has like this been simplified procedure greatly, and has guaranteed that the each several part slit is evenly and on same straight line.
Integrated electrode processing method is particularly useful for electrode to be divided into the situation of a plurality of parts, and the RF electrode of the multipurpose large-capacity linear ion trap that the application proposed just can adopt this method to process.In the existing processing method, usually adopt metal material directly to process the electrode of various piece, adopt insulating material with the each several part combine and assemble then, this just requires to possess accurate mounting technology, and this technology has become a big bottleneck of present ion trap processing and manufacturing.Adopt incorporate processing mode, can guarantee the uniformity of various piece on the same electrode, thereby reduce the difficulty of mounting technology.
The present invention is not limited to the concrete structure of the foregoing description, wherein, can adjust end mark that the RF electrode divided and each several part size, ratio as required, the link position of ion source and detector etc., every based on same thinking of the present invention, all belong to scope of the present invention.
Compare with the combined ion trap that existing a plurality of ion traps directly are composed in series, the structure of the multipurpose large-capacity linear ion trap that the application proposes is more simplified, only come comparison from configuration aspects, as if just omitted termination electrode and directly a plurality of RF electrode groups are together in series, yet such omission but can and be made the change that bring brilliance for control, the debugging of ion trap.Aspect control circuit, can save DC or AC signal on the termination electrode between the adjacent trap, the RF electrode be divided into two parts the time, can save the signal of an endcap electrode, as if its superiority is obvious inadequately, but the partial amt that is divided into along with the RF electrode increases, this advantage is just particularly remarkable.The instrument testing aspect, few termination electrode, the trap internal loss of ion will correspondingly reduce, thereby reduces by an influencing factor to instrument performance.At manufacture view, there is not the separation of end cap, just can adopt the processing mode of integrated electrode, reduce the difficulty of assembling aspect.
In a word, the multipurpose large-capacity linear ion trap that the application proposed can roll into one the function of existing single ion trap and combined ion trap, has extensive applicability, for the development in fields such as biology, pharmacy, ion chemistry provides a kind of strong research tool, simultaneously, because its structure is simple relatively, alleviated the task complexity of control and debugging, and can adopt integral processing method, thereby reduce the assembly difficulty of ion trap.This linear ion hydrazine also will promote the development of the analytical technology in fields such as biology, pharmacy, ion chemistry energetically for the development of ion strap mass analyzer and mass spectrometer provides that a kind of adaptability is strong, diverse in function, be easy to process and assemble, the relative cheap practicable embodiment of cost.
Claims (6)
1. multipurpose large-capacity linear ion trap comprises: the RF electrode group and the determined ion trap of the pair of end electrode chamber that are made of at least four RF electrodes that are parallel to ion trap central shaft Z axle; RF radiofrequency signal and DC direct current signal is characterized in that:
Described RF electrode group comprises two sub-RF electrode groups at least along the Z direction, offers slit on the X electrode pair of each sub-RF electrode group, and slit is used for sample or ion radially injects or outgoing;
Each part of described RF electrode group all is connected with RF radiofrequency signal or DC direct current signal, or the composite signal of the two;
Described termination electrode is the plate electrode of placing along the XY plane, or for to be parallel to the multipole bar of Z axle, or be the combination of plate electrode and multipole bar;
Wherein, the RF electrode of described RF electrode group is divided into: cover the part of metal film and remove the part of the nonmetallic materials matrix surface of metal film at the nonmetallic materials matrix surface, make RF electrode group comprise two sub-RF electrode groups at least along the Z direction thus.
2. multipurpose large-capacity linear ion trap according to claim 1 is characterized in that: at least one described dull and stereotyped termination electrode comprises aperture or slit, is used for the injection or the outgoing of sample or ion.
3. multipurpose large-capacity linear ion trap according to claim 1 is characterized in that: AC voltage is connected to the X electrode pair or the Y electrode pair of sub-RF electrode group, realizes exciting or evict from ion along directions X or Y direction.
4. multipurpose large-capacity linear ion trap according to claim 1 is characterized in that: employed ion source is outer ion source or internal ion-source, or the combination of the two.
5. multipurpose large-capacity linear ion trap according to claim 1 is characterized in that: use two ion sources at least.
6. multipurpose large-capacity linear ion trap according to claim 1 is characterized in that: described nonmetallic materials are pottery, and it is the conductor material of main component that described metal film adopts with the gold.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN2006100649169A CN101038852B (en) | 2006-03-17 | 2006-03-17 | Multipurpose large-capacity linear ion trap and integrated electrode processing method |
| PCT/CN2007/000887 WO2007107106A1 (en) | 2006-03-17 | 2007-03-19 | Multipole linerar ion trap system and method of manufacturing the same with electrodes all-in-one |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2006100649169A CN101038852B (en) | 2006-03-17 | 2006-03-17 | Multipurpose large-capacity linear ion trap and integrated electrode processing method |
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| CN101038852B true CN101038852B (en) | 2011-03-30 |
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| WO (1) | WO2007107106A1 (en) |
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| CN101126738B (en) * | 2007-09-29 | 2011-03-16 | 宁波大学 | Step electrode quadrangular frustum pyramid four-stage quality analyzer |
| US8173976B2 (en) * | 2009-07-24 | 2012-05-08 | Agilent Technologies, Inc. | Linear ion processing apparatus with improved mechanical isolation and assembly |
| CN102231356B (en) * | 2009-12-01 | 2015-03-11 | 株式会社岛津制作所 | Linear ion trap analyzer |
| CN102169791B (en) * | 2010-02-05 | 2015-11-25 | 岛津分析技术研发（上海）有限公司 | A kind of cascade mass spectrometry device and mass spectrometric analysis method |
| CN102103974B (en) * | 2010-12-31 | 2013-02-20 | 聚光科技(杭州)股份有限公司 | Method and device for enhancing CID (Collision Induced Dissociation) property of ion trap |
| CN102163531B (en) * | 2011-03-10 | 2013-01-09 | 中国科学院合肥物质科学研究院 | Flat line type ion trap mass analyzer based on MEMS (micro electro mechanical system) process and manufacturing method thereof |
| CN103718270B (en) * | 2011-05-05 | 2017-10-03 | 岛津研究实验室（欧洲）有限公司 | The device of electrified particle |
| CN102565179B (en) * | 2011-12-31 | 2015-04-29 | 聚光科技(杭州)股份有限公司 | Mass spectrographic analysis method |
| CN103227095B (en) * | 2012-01-31 | 2016-06-08 | 上海华质生物技术有限公司 | Linear ion trap structure |
| CN106062919B (en) * | 2013-08-13 | 2018-05-04 | 普度研究基金会 | Sample is carried out using micro mass spectrometer instrument to quantify |
| US9805923B2 (en) * | 2014-05-16 | 2017-10-31 | Flir Detection, Inc. | Mass separators, mass selective detectors, and methods for optimizing mass separation within mass selective detectors |
| WO2016023215A1 (en) * | 2014-08-15 | 2016-02-18 | 中国计量科学研究院 | Novel rectangular ion trap apparatus and method for storing and separating ions |
| CN105428201A (en) * | 2015-12-25 | 2016-03-23 | 复旦大学 | Stepped electrode ion trap mass analyzer |
| CN105869986B (en) * | 2016-05-04 | 2017-07-25 | 苏州大学 | A kind of mass spectrometry system for improving ion detection efficiency |
| CN106736310B (en) * | 2017-02-27 | 2019-01-11 | 尹智勇 | The preparation method of linear ion hydrazine analyzer |
| CN109256317A (en) * | 2017-07-12 | 2019-01-22 | 赵晓峰 | A kind of device and method storing and transmitting negative ions |
| CN108198743B (en) * | 2018-01-11 | 2020-03-06 | 清华大学深圳研究生院 | Vacuum ionization discontinuous sample introduction method for gas detection |
| CN108806817A (en) * | 2018-06-04 | 2018-11-13 | 中国科学院武汉物理与数学研究所 | A kind of integrated blade trap device for ion-beam cleaning |
| CN109346396B (en) * | 2018-10-09 | 2020-12-01 | 苏州大学 | Mass spectrum system capable of improving ion detection efficiency |
| CN110534385A (en) * | 2019-09-09 | 2019-12-03 | 中国科学院合肥物质科学研究院 | A kind of electric quadrupole lens group with integrated membrane-electrode stick |
| WO2021056394A1 (en) * | 2019-09-27 | 2021-04-01 | 瑞湾科技（珠海）有限公司 | Ion control apparatus |
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| CN1351359A (en) * | 2000-11-01 | 2002-05-29 | 株式会社村田制作所 | Electronic element and manufacture thereof |
| US6838666B2 (en) * | 2003-01-10 | 2005-01-04 | Purdue Research Foundation | Rectilinear ion trap and mass analyzer system and method |
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| CN101038852A (en) | 2007-09-19 |
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